A continuous wave external cavity quantum cascade laser ͑EC-QCL͒ operating between 1872 and 1958 cm −1 has been used to make rotationally resolved measurements in the fundamental band of nitric oxide at 140 mTorr, and the 2 band of water at atmospheric pressure. These measurements demonstrate the advantages of wide tunability and high resolution of the EC-QCL system. From direct absorption spectroscopy on nitric oxide a laser bandwidth of 20 MHz has been deduced and a sensitivity of 8.4ϫ 10 −4 cm −1 Hz −1/2 was achieved. Wavelength modulation spectroscopy using current modulation enhances the sensitivity by a factor of 23 to 3.7ϫ 10 −5 cm −1 Hz −1/2 .

This paper demonstrates how a quantum cascade laser (QCL) in its intrapulse mode can provide a simple method for probing the products of a photolysis event. The system studied is the 266 nm photodissociation of CF3I with the CF3 fragments subsequently detected using radiation at approximately 1253 cm(-1) generated by a pulsed QCL. The tuning range provided by the frequency down-chirp of the QCL operated in its intrapulse mode allows a approximately 1 cm(-1) segment of the CF3 nu3 band to be measured following each photolysis laser pulse. Identification of features within this spectral region allows the CF3 ( v = 0) number density to be calculated as a function of pump-probe delay, and consequently the processes which populate and deplete this quantum state may be examined. Rate constants for the population cascade from higher vibrational levels into the v = 0 state, k 1, and for the recombination of the CF3 radicals to form C2F6, k2, are measured. The returned values of k1 = (2.3 +/- 0.34) x 10(-12) cm(3) molecule(-1) s(-1) and k2 = (3.9 +/- 0.34) x 10(-12) cm(3) molecule(-1) s(-1) are found to be in good agreement with reported literature values.

We review the use of both pulsed and continuous wave quantum cascade lasers in high-resolution spectroscopic studies of gas phase species. In particular, the application of pulsed systems for probing kinetic processes and the inherent rapid passage structure that accompanies observations of low-pressure samples using these rapidly chirped devices are highlighted. Broadband absorber spectroscopy and time-resolved concentration measurements of short-lived species, respectively exploiting the wide intrapulse tuning range and the pulse temporal resolution, are also mentioned. For comparison, we also present recent sub-Doppler Lamb-dip measurements on a low-pressure sample of NO, using a continuous wave external cavity quantum cascade laser system. Using this methodology the stability and resolution of this source is quantified. We find that the laser linewidth as measured via the Lambdip is ca. 2.7 MHz as the laser is tuned at comparably slow rates, but decreases to 1.3 MHz as the laser scan rate is increased such that the transition is observed at 30 kHz. Using this source, wavelength modulation spectroscopy of NO is presented.

A widely tunable pulsed external cavity quantum cascade laser operating around 8 μm has been used to make rotationally resolved measurements of rapid passage effects in the absorption spectrum of N2O. Rapid passage signals as a function of laser power and N2O pressure are presented. Comparisons are drawn with measurements performed on the same transition with a standard distributed feedback quantum cascade laser. The initial observations on rapid passage effects induced with an external cavity quantum cascade laser show that such high power, widely tunable radiation sources may find applications in both nonlinear optics and optical sensing experiments.

Two 5 µm continuous wave quantum cascade lasers are used to perform a counterpropagating pump and probe experiment on a low pressure sample of nitric oxide. The strong pump field excites a fundamental rovibrational transition and the weaker probe field is tuned to the corresponding rotationally resolved hot band transition. When both light fields are in resonance, rapid passage is observed in the hot band absorption lineshape arising from a minimally damped and velocity-selected sample of molecules in the v=1 state. The measured rapid passage signals are well described by a two-level model based on the optical Bloch equations.